Process for producing metal thin films by ALD

ABSTRACT

The invention relates generally to processes for producing electrically conductive noble metal thin films on a substrate by atomic layer deposition. According to one embodiment of the invention a substrate with a surface is provided in a reaction chamber and a vaporised precursor of a noble metal is pulsed into the reaction chamber. By contacting the vaporised precursor with the surface of the substrate, no more than about a molecular layer of the metal precursor is formed on the substrate. In a next step, a pulse of molecular oxygen-containing gas is provided in the reaction chamber, where the oxygen reacts with the precursor on the substrate. Thus, high-quality metal thin films can be deposited by utilising reactions between the metal precursor and oxygen. In one embodiment, electrically conductive layers are deposited in structures that have high aspect ratio vias and trenches, local high elevation areas or other similar surface structures that make the surface rough.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] This invention relates generally to methods of manufacturingnoble metal (Ru, Rh, Pd, Ag, Re, Os, Ir, Pt) layers, such as for use inintegrated circuits (IC) and magnetic recording media.

[0003] 2. Description of the Related Art

[0004] Ruthenium metal is considered to be one of the most promisingmaterials for capacitor electrodes of dynamic random access memories(DRAMs) that have for example Ta₂O₅ and/or (Ba,Sr)TiO₃ (BST) dielectricsruthenium is also a potential electrode material for nonvolatileferroelectric memories. Although platinum has been widely used as anelectrode material, many disadvantages are connected to that concept,For instance, it is very difficult to pattern platinum layers by etchingand platinum catalyses the dissociation of O₂ into atomic oxygen. Theformed oxygen thereof diffuses into the underlying barrier, which getsoxidised and forms a resistive layer. On the contrary, ruthenium filmscan be easily patterned by etching and they prevent oxygen diffusion byforming RuO₂, which has good conductivity. Furthermore, because of itslarge work function, Ru is an interesting electrode material for thefuture CMOS transistors where SiO₂ will be replaced by high-kdielectrics. Though Ru, and for the same reason Ir, are the bestcandidates in what comes to the oxygen diffusion barrier properties,other noble metals, like Pt and Pd, are still considered as viablecandidates for the above applications. With reference to the definitionof noble metal, Encyclopedia Britannica states that a noble metal is anyof several metallic chemical elements that have outstanding resistanceto oxidation, even at high temperatures; the grouping is not strictlydefined but usually is considered to include rhenium, ruthenium,rhodium, palladium, silver, osmium, iridium, platinum, and gold; i.e.,the metals of groups VIIb, VIII, and Ib of the second and thirdtransition series of the periodic table of elements.

[0005] In addition to electrode applications, thin Ru films fundpotential use in the fixture in magnetic recording technology where theever-increasing storage densities set increasing demands on both theread and write heads and recording medium (E. E. Fullerton, Solid StateTechnology, September 2001, p. 87). In anti-ferromagnetically coupledrecording medium, for example, a three atomic layer thick Ru film isused for separating two ferromagnetic layers. In a longer term,perpendicular recording systems (magnetization perpendicular to the filmplane) are expected to replace the current in-plane or longitudinalmedia. To create a high performance recording media with themagnetization perpendicular to the film plane, multilayer structurescomposed of ultra-thin (typically less than 5 atomic layers thick)magnetic and nonmagnetic layers have been suggested. Here Ru and fd, forexample, could be employed as nonmagnetic materials. An evidentchallenge for these magnetic recording media applications is how tocontrol the film thicknesses at an atomic layer level uniformly overlarge substrate areas.

[0006] The current metallisation technology of integrated circuits isbased on electroplated copper. However, a successful electrodepositionprocess requires an appropriate seed layer on the diffusion barriermaterial. Typically copper itself, most often deposited by physicalvapour deposition methods, is used as a seed layer material. Chemicalmethods, like chemical vapour deposition and atomic layer deposition,which could provide better step coverage for the copper seed layer,usually suffer from a poor copper to diffusion barrier adhesion.Further, a general problem related to copper seeds is their easyoxidation, which necessitates a reduction step in the beginning of theelectrodeposition process. As noble metals do not oxidise easily ontheir surface, they can serve as good seed layers for copperelectrodeposition.

[0007] Currently, Ru films are deposited either by sputtering or bychemical vapour deposition (CVD). ALD processes for depositing Ru filmshave not been reported, although the characteristics of thin filmsdeposited by ALD, especially excellent step coverage (conformality),accurate and simple thickness control and large-area uniformity, arevery valuable features in the above mentioned applications.

[0008] The main problem in the development work of depositing metals byALD has been a lack of effective reducing agents, since the metalprecursors applicable in ALD are typically compounds, where the metal isat a higher oxidation state (M. Ritala and M. Leskela, Atomic LayerDeposition, in Handbook of Thin Film Materials, Ed. H. S. Nalwa,Academic Press, San Diego (2001), Vol. 1, Chapter 2, p. 103). A commonstrategy has been to look for reducing agents that, besides reducing themetal, remove the ligands of the metal compound intact, most typicallyin a protonated form. The most simple of such a reaction is the processwhere hydrogen radicals are used as the reducing agent (A. Sherman, U.S.Pat. No. 5,916,365):

[0009] ML_(n)(g)->ML_(n−x)(chemisorbed), where x 0 . . . n−1

[0010] ML_(n−x) (chemisorbed)+(n−x) H(g)->M(s)+(n−x)HL(g)

[0011] Other reducing agents studied for ALD include disilane, diborane,hydrogen, formaldehyde and elemental zinc in the latter case, zincremoves the halide ligands in the form of volatile zinc halide, e.g.ZnCl₂.

[0012] Aoyama et al. (Jpn. J. Appl. Phys. 38 (1999) pp. 2194-2199)investigated a CVD process for depositing ruthenium thin films forcapacitor electrode purposes. They used bis-(cyclopentadienyl)ruthenium(Ru(Cp₂)) as ruthenium precursor and O₂ as reactive gas for decomposingRu(Cp₂) gas. The growth temperature was varied from 230 to 315° C. andthe growth rate was 25 nm/min at 315° C. However, carbon and hydrogenwere incorporated as harmful impurities in the deposited films, thusincreasing the resistivity of the film. Furthermore, the generallimitations of the GVD method, such as problems related to achievinggood large area uniformity and accurate thickness control, still remain.In addition, it is hard to obtain good step coverage and high filmpurity at the same time.

SUMMARY OF THE INVENTION

[0013] The present invention aims at eliminating the problems of priorart and to provide a novel method of producing metal thin films by ALD.

[0014] In particular, it is an object of the present invention toprovide processes for producing electrically conductive noble metal thinfilm on a substrate by atomic layer deposition methods.

[0015] It is a third object of the invention to provide methods ofproducing ultra-high density magnetic recording devices.

[0016] These and other objectives, together with the advantages thereofover known processes, which shall become apparent from the followingspecification, are accomplished by the invention as hereinafterdescribed and claimed.

[0017] Now, we have invented novel processes for depositing metal thinfilms by ALD. In general, the present invention is suitable fordepositing noble metal thin films, such as ruthenium, rhodium,palladium, silver, rhenium, osmium, iridium and platinum.

[0018] The resulting ALD-grown thin metal films may be utilised, forexample, in IC's, e.g. as capacitor electrodes, as gate electrodes andas seed layers for copper metallization, as well as nonmagnetic layersin magnetic media for separating ferromagnetic layers.

[0019] In the preferred embodiment of the present invention a vaporisedprecursor of a noble metal is pulsed into a reaction chamber, where itis contacted with the surface of a substrate placed in the reactionchamber to form a molecular layer of the metal precursor on thesubstrate. The reaction chamber is purged to remove excess vaporisedmetal precursor. Surprisingly we have now found that oxygen, inparticular oxygen in molecular form, is capable of reducing noble metalcompounds into elemental form. High, quality metal thin films can bedeposited by utilising reactions between the metal precursor and oxygen.This is surprising, since oxygen is usually considered an oxidisingsource chemical in ALD and even as such an agent its reactivity isusually only modest at temperatures below 500° C. Clearly, the reductionmechanism described herein differs from the earlier examined ALD metalprocesses, where the ligands are removed intact. In the processesdisclosed herein, oxygen apparently burns the ligands into carbon oxidesand water and, surprisingly, reduces the metal instead of forming ametal oxide, even with those metals (like Ru) that are known to havestable oxides. Thus, in the preferred embodiment the substratecomprising the adsorbed noble metal precursor is contacted with areactant gas that comprises oxygen, preferably free oxygen and morepreferably molecular oxygen. For instance, ruthenium and platinumcompounds that are chemisorbed on the substrate surface can be reducedinto elemental metal by using oxygen, or by providing oxygen into thereaction chamber by decomposing oxygen containing precursors, such asH₂O₂, into oxygen inside the reactor. Since ruthenium and platinum arenoble metals, it can be concluded that oxygen could transformchemisorbed precursors of other noble metals into elemental form aswell. Naturally, for metals that have less positive potential relativeto the hydrogen electrode than noble metals such a mechanism cannot beexpected, as these metals form more stable oxides than the noble metals.

[0020] In one embodiment, electrode layers comprising noble metals areformed in capacitor structures of integrated circuits. In a furtherembodiment, extremely thin films of noble metals which act asnonmagnetic separation layers are used in producing ultrahigh densitymagnetic recording devices.

[0021] More specifically, in the preferred embodiment an electricallyconductive noble metal thin film on a substrate is produced by placing asubstrate in a reaction chamber within a reactor, providing a vaporizednoble metal precursor into the reaction chamber to form a singlemolecular layer of the precursor on the substrate, removing excessvaporized precursor from the reaction chamber providing a secondreactant gas comprising oxygen to the reaction chamber such that theoxygen reacts with the precursor on the substrate, removing excessreactant gas and reaction by-products from the reaction chamber; andrepeating until a thin film of the desired thickness is obtained.

[0022] In one embodiment a capacitor structure is produced by depositinga first insulating layer on a silicon substrate having a doped, placinga conductive material through the insulating layer to contact thesubstrate, depositing a barrier layer over the exposed surface of theconductive material, depositing a first electrode layer comprising anoble metal on the barrier layer by an atomic layer deposition process,depositing a second insulating layer on the first electrode layer, anddepositing a second electrode layer comprising a noble metal on thesecond insulator by an atomic layer deposition process. In anotherembodiment an ultra-high density magnetic recording device is producedby forming a first ferromagnetic recording layer on a substrate, forminga non-magnetic layer consisting essentially of a noble metal on thefirst ferromagnetic recording layer by an atomic layer depositionprocess, and forming a second ferromagnetic recording layer on thenon-magnetic layer.

[0023] A number of considerable advantages are obtained with the aid ofthe present invention. The well-known advantageous characteristics ofALD (accurate and simple control of film thickness, excellent stepcoverage, i.e. conformality, and large area uniformity) can be obtainedfor deposition of metal thin films. The processes of the presentinvention provide a method of producing high quality conductive thinfilms with excellent step coverage. The processes are particularlybeneficial for making electrically conductive layers in structures thathave high aspect ratio vias and trenches, local high elevation areas orother similar surface structures that make the surface rough. Thepresent vapour phase processes are easily integrated into currentprocess equipment, such as that used for the manufacture of integratedcircuits (IC) or magnetic recording media.

[0024] The amount of impurities present in the metal films depositedaccording to the processes of the present invention is low, which isessential when aiming at high conductivity of the film. The amounts ofH, C and N impurities are typically in the order of 0.1 to 0.3 at-%. Theamount of residual oxygen is typically in the range of 0.3 to 0.5 at-%.

[0025] The uniformity of the films and reproducibility of the processescan surprisingly be improved by providing the substrate surface withhydroxyl groups. Such a hydroxyl group rich surface, which promotesnucleation, can be realised very easily by depositing an ultra-thinlayer of metal oxide, such as Al₂O₃ or TiO₂. In one embodiment the layerof metal oxide is deposited by ALD by using H₂O and/or H₂O₂ as an oxygensource.

BRIEF DESCRIPTION OF THE DRAWINGS

[0026]FIG. 1 shows the growth rate and resistivity of ruthenium thinfilms as a function of the evaporation temperature of the rutheniumprecursor.

[0027]FIG. 2 shows the growth rate and resistivity of ruthenium thinfilms as a function of the growth temperature.

[0028]FIG. 3 is a schematic side view of the stricture of a DRAMcapacitor before the formation of a conductor peg.

[0029]FIG. 4 is a schematic side view of the structure of a DRAMcapacitor after the formation of a conductor peg and the deposition ofcapacitor thin films.

[0030]FIG. 5 is a schematic side view of the structure of a DRAMcapacitor before the formation of a capacitor hollow.

[0031]FIG. 6 is a schematic side view of the structure of a DRAMcapacitor after the formation of a capacitor hollow and the depositionof capacitor thin films.

[0032]FIG. 7 is a schematic side view of the structure of a DRAM trenchcapacitor.

[0033]FIG. 8 is a schematic side view of magnetic recording plate thatshows the position of a non-magnetic separator film.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

[0034] The present invention relates generally to methods of producingthin films by atomic layer deposition (ALD) processes. According totypical ALD methods a substrate with a surface is placed in a reactionchamber, the substrate is heated up to suitable deposition temperatureat lowered pressure, a first reactant is conducted in the form of gasphase pulses (in the following also: “gaseous reactant is pulsed”) intothe reaction chamber and contacted with the surface of the substrate tobind or absorb no more than about one monolayer of the reactant onto thesurface, excess of the first reactant is purged out of the reactionchamber in vaporous or gas form, a second gaseous reactant is pulsedonto the substrate to provide a surface reaction between the secondreactant and the first reactant bound to the surface, excess of thesecond reactant and gaseous by-products of the surface reactions arepurged out of the reaction chamber, and the steps of pulsing and purgingare repeated in the indicated order until the desired thickness of thedepositing thin film is reached. The method is based on controlledsurface reactions of the precursor chemicals. Gas phase reactions areavoided by feeding reactants alternately into the reaction chamber.Vapour phase reactants are separated from each other in the reactionchamber by removing excess reactants and/or reactant by-products fromthe reaction chamber, such as with an evacuation step and/or with aninactive gas pulse (e.g. nitrogen or argon).

[0035] According to the preferred embodiment, a noble metal thin film isproduced on a substrate surface by a process comprising at least thefollowing steps:

[0036] providing a substrate with a surface into a reaction chamber,

[0037] pulsing a vaporised precursor of the noble metal into thereaction chamber to form a molecular layer of the metal precursor on thesubstrate,

[0038] purging the reaction chamber to remove excess vaporised noblemetal precursor,

[0039] providing a pulse of oxygen containing gas onto the substrate,

[0040] purging the reaction chamber to remove excess of the oxygencontaining gas and the gaseous by-products formed in the reactionbetween the metal precursor layer on the substrate and the oxygen, and

[0041] repeating the pulsing and purging steps until desired thicknessof the depositing thin film is reached.

[0042] According to another embodiment of the present invention thefinal metal structure may consist of two or more different noble metallayers on top of each other. For example, the growth can be started withthe deposition of platinum and ended with the deposition of rutheniummetal.

[0043] The substrate can be of various types of material. Whenmanufacturing integrated circuits, the substrate preferably consists ofnumerous thin films with varying chemical and physical properties. Thesurface of the substrate may be a dielectric layer, such as Ta₂O₅ or(Ba,Sr)TiO₃. Further, the substrate surface may have been patterned andit therefore consists of small (less than 1 μm) nodes, vias and/ortrenches with a very high aspect ratio, approximately from 2:1 up to150:1 and even higher.

[0044] Thus, in the preferred process for producing a capacitorstructure in integrated circuits, the noble metal layer is preferablydeposited on a barrier layer comprising, for example, a metal nitride.In one embodiment that process comprises

[0045] providing a silicon substrate having a doped region, which formsthe active part of a transistor;

[0046] depositing a first insulator layer on the substrate;

[0047] placing a conductor material in contact with the siliconsubstrate so that it extends through the insulator layer forming anexposed surface;

[0048] depositing a barrier layer essentially covering the exposedsurface of the conductor material;

[0049] depositing by atomic layer deposition a first electrode layercomprising a noble metal on the barrier layer;

[0050] depositing a second insulator layer on the first electrode layer;and

[0051] depositing by atomic layer deposition a second electrode layercomprising a noble metal on the second insulator.

[0052] The substrate layer may also comprise a ferromagnetic layer, asin the production of an ultra-high density magnetic recording device,wherein a first and a second ferromagnetic recording layer are formed ona substrate, the second being spaced apart from the first, and aseparation layer comprising a nonmagnetic layer of a noble metal ispreferably deposited by ALD between the first and the secondferromagnetic layers.

[0053] The noble metal precursor employed in the ALD processes may besolid, liquid or gaseous material, provided that the metal precursor isin vapour phase or is evaporated before it is conducted into thereaction chamber and contacted with the substrate surface to bind theprecursor onto the substrate. Pulsing a vaporised precursor onto thesubstrate means that the precursor vapour is conducted into the chamberfor a limited period of time. Typically, the pulsing time is from about0.05 to 10 seconds. However, depending on the substrate type and itssurface area, the pulsing time may be even higher than 10 seconds.

[0054] In the methods of the present invention, suitable metalprecursors for depositing conductive noble metal layers are generallymetal compounds where the metal is bound or coordinated to either oxygenor carbon, and more preferably metallocene compounds and beta-diketonatecompounds of the metals. When depositing ruthenium thin films, preferredmetal precursors are bis(cyclopentadienyl)ruthenium andtris(2,2,6,6-tetramethyl-3,5-heptanedionato)ruthenium(M) and theirderivatives, such as bis(pentamethylcyclopentadienyl)ruthenium andbis(2,2,6,6-tetramethyl-3,5-heptanedionato)(1,5-cyclooctadiene)ruthenium(II).When depositing platinum films, preferred metal precursors are(trimethyl)methylcyclopentadienylplatinum(IV), platinum (II)acetylacetonato, bis(2,2,6,6-tetramethyl-3,5-heptanedionato)platinum(TI)and their derivatives.

[0055] Purging the reaction chamber means that gaseous precursors and/orgaseous byproducts formed in the reaction between the precursors areremoved from the reaction chamber, such as by evacuating the chamberwith a vacuum pump and/or by replacing the gas inside the reactor withan inert gas (purging), such as argon or nitrogen. Typical purging timesare from about 0.05 to 20 seconds.

[0056] The oxygen containing pulse can be provided by pulsing oxygen ora mixture of oxygen and another gas into the reaction chamber, or byforming oxygen inside the, reactor by decomposing oxygen containingchemicals, such as H₂O₂, N₂O and/or an organic peroxide. For example,the catalytical formation of an oxygen containing pulse can be providedby introducing into the reactor a pulse of vaporised aqueous solution ofH₂O₂ and conducting the pulse over a catalytic surface inside thereactor and thereafter into the reaction chamber. For instance, thecatalytic surface may preferably be a piece of platinum or palladium.

[0057] The oxygen pulse is preferably a free-oxygen containing gaspulse, more preferably a molecular oxygen-containing gas pulse and cantherefore consist of a mixture of oxygen and inactive gas, for example,nitrogen or argon. Preferred oxygen content of the oxygen-containing gasis from about 10 to 25%. Therefore, one preferred source of oxygen isair. In the case of relatively small substrates (e.g., up to 4-inchwafers) the mass flow rate of the oxygen-containing gas is preferablybetween about 1 and 25 sccm, more preferably between about 1 and 8 sccm.In case of larger substrates the mass flow rate of oxygen-containing gasis scaled up.

[0058] The pressure in the reaction space is typically between about0.01 and 20 mbar, more preferably between 1 and 10 mbar.

[0059] Before starting the deposition of the film, the substrate istypically heated up to a suitable growth temperature. Preferably, thegrowth temperature of metal thin film is approximately from about 200 to500° C., more preferably from about 300 to 360° C. for Ru, and fromabout 250 to 400° C. for Pt.

[0060] The processing time depends on the thickness of the layer to beproduced and the growth rate of the film. In ALD, the growth rate of athin film is determined as thickness increase per one cycle. One cycleconsists of the pulsing and purging steps of the precursors and theduration of one cycle is typically between about 0.2 and 30 seconds,

[0061] Examples of suitable arrangements of reactors used for thedeposition of thin films according to the processes of the presentinvention are, for instance, commercially available ALD equipment, suchas the F-120 and Pulsar™ reactors, produced by ASM Microchemistry Ltd.In addition to these ALD reactors, many other kinds of reactors capablefor ALD growth of thin films, including CVD reactors equipped withappropriate equipment and means for pulsing the precursors, can beemployed for carrying out the processes of the present invention. Thegrowth processes can optionally be carried out in a cluster tool, wherethe substrate arrives from a previous process step, the metal film isproduced on the substrate, and then the substrate is transported to thefollowing process step. In a cluster tool, the temperature of thereaction space can be kept constant, which clearly improves thethroughput compared to a reactor in which is the substrate is heated upto the process temperature before each run.

[0062] A stand-alone reactor can be equipped with a load-lock. In thatcase, it is not necessary to cool down the reaction space between eachrun.

[0063] In one embodiment the present invention provides processes forthe deposition of capacitor electrodes. A silicon substrate 30 isprovided, with a doped region 34 that is an active part of a transistor.Field oxide 32 separates the transistors from each other. An insulatorlayer 36, e,g., SiO₂, is grown on the substrate. The insulator isplanarized. A resist layer 38 is formed on the insulator layer 36 andpatterned so that an opening 40 is formed. Vias are etched to theinsulator and the via is filled with a conductor material 50, e.g.polysilicon. Polysilicon layer is patterned and etched so that the viaplug and a tooth-like extension over the plug remain on the structure.The polysilicon tooth minimizes the amount of expensive metal that isneeded for the lower electrode. Exposed surface of the polysilicon maybe very rough after the etching step so that the surface area ofpolysilicon is as large as possible. A barrier layer 52, e.g. tantalumsilicon nitride Ta_(x)Si_(y)N_(z) is deposited over the substrate bye.g. Atomic Layer Deposition (ALD). The barrier layer is patterned andetched so that there is barrier layer left only on and near thepolysilicon surface.

[0064] A noble metal, e.g. Pt or Ru, is grown by ALD on the substrateand then the metal layer is patterned and etched so that there is metal54 left only on and near the barrier layer 52. After that a capacitorinsulator 56 is deposited on the substrate. The capacitor insulator 56preferably has a high dielectric constant, i.e. it is a high-k material.A high-k material preferably has a k value ≧5, more preferably ≧10, evenmore preferably ≧20. Barium-strontium titanate (3ST) and tantalum oxideTa₂O₅ serve as examples of suitable high-k materials. The high-k layeris optionally annealed to increase the crystallinity and dielectricconstant of the layer. Finally, an upper electrode 58, e.g. Ru or Pt isdeposited on the high-k material 56, and patterned and etched so thatthe capacitor can be addressed (electrically accessed).

[0065] Another way of constructing the capacitor is to planarize thesubstrate surface after the deposition of polysilicon and then form ametal knob on polysilicon. However, a relatively thick layer of metal isneeded on the polysilicon plug to increase the effective area of thecapacitor. In that case the metal, e.g. Pt or Ru deposited by ALD, formsthe part of the “tooth” that extends above the insulator 36 plane.

[0066] Another way of increasing the effective area of the capacitor isto etch a hollow on a surface and form a capacitor structure on thewalls and the bottom of the hollow. As shown in FIG. 5, there is apolysilicon plug 50 extending through the first insulator layer 36. Thesecond insulator layer 70 (e.g. SiO₂) is deposited on the firstinsulator layer and polysilicon plug. A resist 72 placed on the surfaceof the second insulator 70 is patterned so that an opening 74 can beformed over the polysilicon plug 50. Referring to FIG. 6, the secondinsulator is etched until a capacitor hollow 96 is formed. Residualresist is removed. Then a barrier layer, e.g. Ta_(x)Si_(y)N_(z) isdeposited on the substrate and patterned so that only the top surface ofthe polysilicon plug is covered with the barrier 76. A lower metalelectrode, e.g. Pt or Ru, is deposited by ALD on the substrate andpatterned and etched so that only the bottom and the walls of the holloware covered with the lower metal electrode 90. High-k dielectric layer92, e.g. BST is grown on the substrate by e.g. ALD. An optionalannealing step may be used to increase the crystallinity and dielectricconstant of the dielectric layer 92. Finally, the upper metal electrode94, e.g., Pt or Ru, is deposited by ALD on the high-k thin film 92according to the present invention.

[0067] Still another way of increasing the effective area of the DRAMcapacitor while keeping the reserved substrate area to a minimum is toplace the capacitor structure in a deep pit etched on silicon substrate.The structure is called a trench capacitor. FIG. 7 shows a trenchcapacitor without the addressing lines and semiconducting activecomponents. On silicon substrate 110 there is a trench with a surfacethat has been covered with a multi-layer thin film 112. The depositionhas started with the formation of a barrier layer 114, e.g.Ta_(x)Si_(y)N_(z), which is preferably formed between the silicon andplatinum group metals or ruthenium to prevent the formation of metalsilicides. On the barrier layer 114 a first metal electrode 116, e.g. Ptor Ru, is grown according to the present invention by ALD. On the firstmetal electrode layer 116 a high-k layer 118, e.g. BST, is grown e.g. byALD. On the high-k layer 118 a second metal electrode layer 120, e.g. Ptor Ru, is grown according to the present invention by ALD. In the casewhere the trench will be filled with polysilicon 124, it is preferableto protect the second metal electrode 120 with a barrier thin film 122,e.g. Ta_(x)Si_(y)N_(z).

[0068] The thickness of the metal electrode can be selected fromapproximately 1 μm up to about 200 nm and even more depending on theapplication.

[0069] Optionally, the deposition process can be enhanced by initiatingthe growth by providing the substrate surface with hydroxyl groups. Inone embodiment a thin initiating layer of a metal oxide, such as Al₂O₃or TiO₂, is deposited before starting the growth of the metal film.Fragments of ammonia attached to the surface, i.e. —NH₂ and ═NH groups,may also serve as nucleation points for the metal deposition. A layer of10 Å to 20 Å of the oxide is capable of providing the desiredimprovement in the metal deposition process, i.e. the reproducibility ofthe process and the uniformity of the films is improved. If the metaldeposition 58 is preceded by a dielectric deposition, such as(Ba,Sr)TiO₃ 56 in the case of DRAMS or ZrO₂ or HfO₂ in the case of CMOStransistors, and that process leaves the dielectric surface covered withhydroxyl groups, no separate hydroxylation step is required. Examples ofsuch dielectric deposition processes are all water based ALD oxideprocesses. Further, a hydroxyl-group deficient surface can bere-hydroxylated with reactive compounds, such as hydrogen peroxide(H₂O₂). This is advantageous, for example, in cases where it is notpossible to grow an insulating layer prior to the deposition of themetals of the present invention.

[0070] In the case of ultrahigh density magnetic recording it isadvantageous to divide the ferromagnetic recording layer on a substrate150 with a nonmagnetic layer 154, e.g. Ru, into two parts 152 and 156 inthe thickwise direction. As a result, the stability of the magneticpolarization state of very small magnetic bits on the surface isenhanced and spontaneous random flipping of the magnetic polarizationstate is avoided. Ru film 154 that helps to form antiferromagneticallycoupled media is deposited according to the present invention.

[0071] According to still another embodiment of the present invention,the a seed layer is deposited that is utilised in dual damascenestructures for the copper metallization of vias and trenches. In thisembodiment a substrate with trenches and vias coated with a diffusionbarrier is provided into the reaction chamber. The seed layer consistingof at least one metal selected from Ru, Rh, Pd, Ag, Re, Os, Ir and Pt isgrown from alternating vapor phase pulses of a metal source chemical andan oxygen source chemical that are separated from each other with anevacuation step and/or an inactive gas (e.g. nitrogen or argon) pulse,as described above. The thickness of the resulting seed layer can befrom approximately 1 nm up to 30 nm or even more depending on thedimensions of the trenches and vias. The seed layer is useful, forexample, as a starting layer for the copper deposition by electroplatingor a CVD process.

[0072] The following non-limiting examples will illustrate the inventionin more detail.

EXAMPLE 1

[0073] Ruthenium thin films were deposited in a flow type F-120 ALDreactor (ASM Microchemistry). Bis(cyclopentadienyl)ruthenium (Ru(Cp)₂)and air (with a flow rate of 8 sccm during the pulses) were used asprecursors. The ruthenium films were deposited on 5×5 cm² borosilicateglass substrates covered by thin Al₂O₃ film. The growth temperature was350° C.

[0074] The Al₂O₃ film was found to be beneficial to obtain uniformruthenium films and a reproducible process. The inventors assume thatthis is due to a high density of reactive sites, such as hydroxyl groups(—OH), on an Al₂O₃ film. The density of such reactive sites is high on afresh surface of an Al₂O₃ thin film that is deposited by ALD. In thisexperiment the thin Al₂O₃ film for initiating proper growth of Ru filmswas produced by ALD by using AlCl₃ and H₂O or H₂O₂ as precursors. Totalamount of 40 cycles of Al₂O₃ was applied.

[0075] The effect of the dose of ruthenium precursor was varied byvarying the evaporation temperature. Therefore the temperature of theopen evaporation boat inside the reactor was varied form 45 to 70° C.The growth rate and the quality of the films were investigated.

[0076] The pulse length of evaporated ruthenium precursor was 0.5seconds and the purge thereafter was 0.5 seconds. The pulse length ofair pulse was 0.2 seconds and the purge thereafter was 0.5 seconds. Thetotal amount of cycles was 3000. The results in FIG. 1 show that thedeposition rate is independent of the RuCp₂ dose as varied through itsvapour pressure, which in turn is varied through its evaporationtemperature. This proves that the film growth proceeds in aself-limiting manner as is characteristic of ALD. Therefore, all theadvantageous features of ALD are available.

EXAMPLE 2

[0077] Ruthenium thin films were deposited in a flow type F-120 ALDreactor (ASM Microchemistry). Bis(cyclopentadienyl)ruthenium (Ru(Cp)₂)and air (with a flow rate of 8 seem during the pulses) were used asprecursors. Ru(Cp)₂ was evaporated from an open boat inside the reactorat 50° C. The ruthenium films were deposited on 5×5 cm² borosilicateglass substrates covered by thin Al₂O₃ film. The growth temperature was350° C.

[0078] The effect of the dose of ruthenium precursor was varied byvarying the pulse length of the evaporated precursor from 0.2 seconds to1.2 seconds. The growth rate and the quality of the films wereinvestigated.

[0079] The purge after the ruthenium pulse was 0.5 seconds. The pulselength of air pulse was 0.2 seconds and the purge thereafter was 0.5seconds. The total amount of cycles was 3000.

[0080] The results in Table 1 show that the deposition rate isindependent of the RuCp₂ dose as varied through its pulse length, whenthe pulse time is longer than 0.2 s. This proves that the film growthproceeds in a self-limiting manner as is characteristic of ALD. TABLE 1Effect of the length of the RuCp₂-pulse Growth Length of Resistivityrate Thickness RuCp₂-pulse (μΩcm) Å/cycle) (Å) 0.2 s 17.9 0.20 400 0.5 s14.4 0.43 860 0.5 s 15.0 0.44 870 0.7 s 14.9 0.47 940 1.0 s 14.1 0.47940 1.2 s 13.9 0.48 960

EXAMPLE 3

[0081] Ruthenium thin films were deposited in a flow type F-120 ALDreactor (ASM Microchemistry). Bis(cyclopentadienyl)ruthenium (Ru(Cp)z)and air were used as precursors. Ru(Cp)₂ was evaporated from an openboat inside the reactor at 50° C. The ruthenium films were deposited on5 cm×5 cm borosilicate glass substrates covered by thin Al₂O₃ film. Thetested growth temperature was 350° C.

[0082] The pulse length of evaporated ruthenium precursor was 0.5seconds and the purge thereafter was 0.5 seconds. The pulse length ofair pulse was 0.2 seconds and the purge thereafter was 0.5 seconds. Thetotal amount of cycles was 2000.

[0083] The effect of the dose of oxygen was tested by varying the airflow rate from 0 to 14 sccm. The growth rate and the quality of thefilms were investigated. The results in Table 2 show that the depositionrate is independent of the air flow above 4 sccm. This proves that thefilm growth proceeds in a self-limiting manner as characteristic to ALD.Further, as the film growth does not proceed without air, it is provedthat the growth is not due to a decomposition of RuCp₂ but due to areaction between RuCp₂ and oxygen. TABLE 2 Effect of air flow rate AirGrowth flow Resistivity rate Thickness rate (μΩcm) (Å/cycle) (Å) 14 sccm12.1 0.35 700  8 sccm 15.0 0.44 870  8 sccm 14.4 0.43 860  4 sccm 14.40.43 860  2 sccm 12.3 0.34 680  L sccm 12.4 0.31 610  O sccm — — No film

EXAMPLE 4

[0084] Ruthenium thin films were deposited in a flow type F-120 ALDreactor (ASM Microchemistry). Bis(cyclopentadienyl)ruthenium (Ru(Cp)₂)and air (with a flow rate of 1 sccm during the pulses) were used asprecursors. Ru(Cp)₂ was evaporated from an open boat inside the reactorat 50° C. The ruthenium films were deposited on 5×5 cm² borosilicateglass substrates covered by thin Al₂O₃ film. The tested growthtemperature was 350° C.

[0085] The pulse length of evaporated ruthenium precursor was 0.5seconds and the duration of the purge thereafter was 0.5 seconds. Thepulse length of air pulse was varied and the purge thereafter was 0.5seconds. The total amount of cycles was 2000.

[0086] The effect of the dose of oxygen was tested by varying the lengthof the air pulse from 0.2 to 2.0 seconds. The flow rate of oxygen was 1sccm. The growth rate and the quality of the films were investigated.The results in Table 3 show that the deposition rate is independent ofthe air pulse length above one second. This proves that the film growthproceeds in a self-limiting manner as characteristic to ALD. TABLE 3Effect of air pulse length Growth Resistivity rate Thickness Air pulselength (μΩcm) (Å/cycle) (Å) 0.2 s 12.4 0.31 610 0.5 s 13.1 0.32 640 0.7s 12.4 0.38 760 1.0 s 12.4 0.39 780 1.0 s 12.5 0.43 860 1.5 s 12.0 0.44880 2.0 s 11.7 0.45 890

EXAMPLE 5

[0087] Ruthenium thin films were deposited in a flow type F-120 ALDreactor (ASM Microchemistry). Bis(cyclopentadienyl)ruthenium (Ru(Cp)₂)and air (with a flow rate of 8 sccm during the pulses) were used asprecursors. Ru(Cp)₂ was evaporated from an open boat inside the reactorat 50° C. The ruthenium films were deposited on 5 cm×5 cm borosilicateglass substrates covered by thin Al₂O₃ film. The tested growthtemperature was 350° C.

[0088] The pulse length of evaporated ruthenium precursor was 0.5seconds and the duration of the purge thereafter was 0.5 seconds. Thepulse length of air pulse was 0.2 seconds and the purge thereafter wasvaried. The total amount of cycles was 2000.

[0089] The effect of the length of the purge after the air pulse wastested by varying the length of the purge from 0.2 to 1.0 seconds. Thegrowth rate and the quality of the films were investigated. Results inTable 4 show that there is no dependence on the purge time, thus provingthat the precursor pulses are well separated. TABLE 4 Effect of thelength of the purge after the air pulse Growth Length of air Resistivityrate Thickness purge (μΩ · cm (Å/cycle) (Å) 0.2 s 12.1 0.41 810 0.5 s14.4 0.43 860 0.5 s 15.0 0.44 870 1.0 s 13.1 0.40 800

EXAMPLE 6

[0090] Ruthenium thin films were deposited in a flow type F-120 ALDreactor (ASM Microchemistry). Bis(cyclopentadienyl)ruthenium (Ru(Cp)₂)and air (with a flow rate of 8 sccm during the pulses) were used asprecursors. Ru(Cp)₂ was evaporated from an open boat inside the reactorat 50° C. The ruthenium films were deposited on 5 cm×5 cm borosilicateglass substrates covered by thin Al₂O₃ film. Again, the Al₂O₃ film wasfound to be beneficial in obtaining smooth and reproducible rutheniumfilms. The tested growth temperature was 350° C.

[0091] The pulse length of evaporated ruthenium precursor was 0.5seconds and the duration of the purge thereafter was varied. The pulselength of air pulse was 0.2 seconds and the purge thereafter was 0.5seconds. The total amount of cycles was 2000.

[0092] The effect of the length of the purge after the Ru(Cp)₂ pulse wastested by varying the length of the purge from 0.2 to 1.0 seconds. Thegrowth rate and the quality of the films were investigated. Results inTable 5 show that there is no dependence on the purge time, thus provingthat the precursor pulses are well separated. TABLE 5 Effect of thelength of the purge after the RuCp₂ pulse Growth Length of purgeResistivity rate Thickness after Ru(Cp)2 (μΩcm) (Å/cycle) (Å) 0.2 s 13.30.40 790 0.5 s 14.4 0.43 860 0.5 s 15.0 0.44 870 1.0 s 12.9 0.38 750

EXAMPLE 7

[0093] Ruthenium thin films were deposited in a flow type F-120^(nm) ALDreactor (ASM Microchemistry). Bis(cyclopentadienyl)ruthenium (Ru(Cp)₂)and air (with a flow rate of 8 sccm during the pulses) were used asprecursors. Ru(Cp)₂ was evaporated from an open boat inside reactor at50° C. The ruthenium films were deposited on 5×5 cm² borosilicate glasssubstrates covered by thin Al₂O₃ film. The tested growth temperatureswere 350 and 300° C.

[0094] The effect of the number of total amount of cycles was tested.The growth rate and the quality of the films were investigated.

[0095] Table 6 and 7 show that as characteristic to ALD, filmthicknesses can be controlled simply but accurately by the number ofdeposition cycles applied. Some initiation period with lower growth rateseems to exist in the beginning of the film growth, however. This can beattributed to the initial nucleation on the oxide surface. TABLE 6Effect of number of cycles at the growth temperature of 350° C. GrowthResistivity rate Thickness Number of cycles (μΩ · cm) (Å/cycle) (Å) 100017.5 0.39 390 1000 15.1 0.35 350 2000 14.4 0.43 860 2000 15.0 0.44 8703000 12.9 0.41 1240 3000 13.3 0.39 1170 4000 11.7 0.41 1620 4000 12.60.44 1740

[0096] TABLE 7 Effect of number of cycles at the growth temperature of300° C. Growth Number of Resistivity rate Thickness cycles (μΩcm)(Å/cycle) (Å) Comments 1000 257 0.09 90 thin, non-uniform film, poorconductivity 2000 19.0 0.18 350 Uniform film with metallic luster 300014.7 0.27 810 Uniform film with metallic luster 4000 12.5 0.29 1150Uniform film with metallic luster

EXAMPLE 8

[0097] Ruthenium thin films were deposited in a flow type F-120 ALDreactor (ASM Microchemistry). Bis(cyclopentadienyl)ruthenium (Ru(Cp)₂)and air (with a flow rate of 8 sccm during the pulses) were used asprecursors. Ru(Cp)₂ was evaporated from an open boat inside the reactorat 50° C. The ruthenium films were deposited on 5 cm×5 cm borosilicateglass substrates covered by thin Al₂O₃ film. Again, the Al₂O₃ film wasfound to be beneficial to obtain uniform ruthenium films and areproducible process. As deposited TiO₂ was found to have such abeneficial effect too.

[0098] In this experiment the thin Al₂O₃ film for promoting nucleationand thereby initiating proper growth of Ru films was produced by ALD byusing AlCl₃ and H₂O or H₂O₂ as precursors. Total amount of 40 cycles ofAl₂O₃ was applied on the surface of the substrate before starting thedeposition of the Ru film.

[0099] The effect of deposition temperature on the growth and thequality of the films was tested. Growth temperatures from 250 to 450° C.were tested as shown in FIG. 2. The content of ruthenium, oxygen,carbon, nitrogen and hydrogen of the films grown at 300, 350° C. and400° C. were measured by time-of-flight elastic recoil detectionanalysis (TOF-FRDA) and the results are shown in Table 8.

[0100] The pulse length of evaporated ruthenium precursor was 0.5seconds and the purge thereafter was 0.5 seconds. The pulse length ofair pulse was 0.2 seconds and the purge thereafter was 0.5 seconds. Thetotal amount of cycles was 3,000. The results shown in Table 1 show thatRu films with low resistivities are obtained over a broad temperaturerange of 275° C.-400° C. From the growth rate and film purity point ofview it is beneficial to use deposition temperatures from 350° C. to400° C. However, already at 300° C. the film purity is remarkable. TABLE8 Composition of the ruthenium thin films by TOF-ERDA Growth temperatureRu O C N H (° C.) at- % at- % at- % at- % at- % 400 ˜100 <0.5 <0.3 <0.1<0.2 350 ˜100 <0.4 <0.2 <0.1 <0.2. 300 ˜100 <1.5 <0.3 <0.1 <0.4

EXAMPLE 9

[0101] Ruthenium thin films were deposited in a flow type F-120 ALDreactor (ASM Microchemistry). Bis(cyclopentadienyl)ruthenium(ruthenocene, Ru(Cp)₂) and 30% hydrogen peroxide solution were used asprecursors. Ru(Cp)₂ was evaporated from an open boat inside the reactorat 75° C. Hydrogen peroxide solution was kept at room temperature andwas introduced into the reactor through needle and solenoid valves. Theruthenium films were deposited on 5 cm×5 cm borosilicate glasssubstrates covered by a thin Al₂O₃ film. The Al₂O₃ film was found to bebeneficial to obtain uniform ruthenium films and a reproducible process.

[0102] The deposition of ruthenium films was carried out according tothe ALD method by pulsing Ru(Cp)₂ and H₂O₂ alternately into the reactor.H₂O₂ was pulsed over a platinum plate to decompose H₂O₂ to O₂. The pulselength of Ru(Cp)₂ was varied between 0.2 and 1.0 s and the pulse lengthof H₂O₂ was varied between 0.5 and 2.0 s. The length of the purge pulsewas always 0.5 s after the Ru(Cp)₂ pulse and 1.5 s after the H₂O₂ pulse.

[0103] The films were grown at 350° C. The deposition mate variedbetween 0.41 and 0.44 Å/cycle when the Ru(Cp)₂ pulse length was variedbetween 0.2 and 1.0 s and the pulse length of H₂O₂ was 2.0 s. When thepulse length of Ru(Cp)₂ was kept constant (0.5 s) and the pulse lengthof H₂O₂ was varied between 0.5 and 2.0 s and the deposition rateincreased from 0.35 to 0.44 A/cycle, respectively. According to the XRDmeasurements the films were polycrystalline ruthenium metal. Theresistivity of the films varied between 10 and 15 μΩcm. The resistivitywas measured by the four-point probe method.

EXAMPLE 10

[0104] Deposition experiments of ruthenium thin films were carried outin a flow type F-120 ALD reactor (ASM Microchemistry).Bis(2,2,6,6-tetramethyl-3,5-heptanedionato) ruthenium(II) (Ru(thd)₂) andair with a flow rate of 25 sccm during the pulses were used asprecursors. Ru(thd)₂ was evaporated from an open boat inside the reactorat 100° C. The ruthenium films were deposited on 5×5 cm² borosilicateglass substrates covered by thin Al₂O₃ film. The deposition temperaturewas either 350 or 400° C. and the growth rates were 0.40 and 0.35Å/cycle, respectively. These growth rates are comparable to thoseobtained with Ru(Cp)₂. The resistivities were 17-18 μΩ.cm. According tothe XRD measurements the films were polycrystalline ruthenium metal.

EXAMPLE 11

[0105] Deposition experiments of ruthenium thin films were carried outin a flow type F-120 ALD reactor (ASM Microchemistry).Bis(2,2,6,6-tetramethyl-3,5-heptanedionato) ruthenium(II) (Ru(thd)₂) and30% hydrogen peroxide water solution were used as precursors. Ru(thd)₂was evaporated from an open boat inside the reactor at 120° C. Hydrogenperoxide solution was kept at room temperature and was introduced intothe reactor through needle and solenoid valves. The ruthenium films weredeposited on 5×5 cm² borosilicate glass substrates covered by thin Al₂O₃film. The deposition temperature was varied between 400 and 500° C. Thefilms had lower growth rate than those deposited from Ru(Cp)₂. Accordingto the XRD measurements the films were polycrystalline ruthenium metal.

EXAMPLE 12

[0106] Platinum thin films were deposited in a flow type F-120 ALDreactor (ASM Microchemistry). (Trimethyi)methylcyclopentadienylplatinum(PtTMCp) and air (with a flow rate of 25 sccm during the pulses) wereused as precursors. PtTMCp was evaporated from an open boat inside thereactor at 21° C. The platinum films were deposited on 5×5 cm²borosilicate glass substrates covered by thin Al₂O₃ film. The growthtemperature was 300° C. Furthermore, it was tested that Pt film grows at250° C., too.

[0107] The pulse length of platinum precursor was 0.5 seconds and thepurge after the platinum precursor pulse was 1.0 seconds. The pulselength of air pulse was varied front 0.5 to 2.0 seconds and the purgethereafter was 2.0 seconds. The total number of cycles was 1500.

[0108] It was found out that platinum films barely grew when the airpulse length was 0.5 seconds. However, the air pulse of only 1.0 secondresulted in uniform film growth at the rate of 0.35 Å/cycle. Theresistivities of the films were measured. The results are shown in Table9. TABLE 9 The effect of air pulse length on the resistivities andgrowth rates of platinum thin films. Growth Length of air pulseResistivity rate Thickness (s) (μΩcm) (Å/cycle) (nm) 1.0 13.9 0.35 521.5 12.4 0.43 65 2.0 12.6 0.45 68

[0109] The variation of the film thickness over the substrate wasnegligible. The thickness variation over 4 cm was within the range ofthe accuracy of the applied measurement method, i.e. ±1 nm.

EXAMPLE 13

[0110] Platinum thin films were deposited as described in Example 12 at300° C. The pulse length of platinum precursor was 0.5 seconds followedby a purge of 1.0 second. The pulse length of air pulse was 1.0 secondand the purge thereafter was 2.0 seconds. The effect of the total numberof cycles on the growth rate was tested with 1500, 2250 and 3000 cycles.

[0111] The resistivities and thicknesses of the films were measured. Theresults are shown in Table 10. TABLE 10 The effect of number of cycleson the resistivities and growth rates of platinum thin films GrowthResistivity rate Thickness Number of cycles (μΩcm) (Å/cycle) (nm) 150013.9 0.35 52 2250 12.4 0.39 78 3000 11.5 0.35 106

[0112] Although the foregoing invention has been described in terms ofcertain preferred embodiments, other embodiments will be apparent tothose of ordinary skill in the art. Moreover, although illustrated inconnection with particular process flows and structures, the skilledartisan will appreciate variations of such schemes for which the methodsdisclosed herein will have utility. Additionally, other combinations,omissions, substitutions and modification will be apparent to theskilled artisan, in view of the disclosure herein. Accordingly, thepresent invention is not intended to be limited by the recitation of thepreferred embodiments, but is instead to be defined by reference to theappended claims.

We claim:
 1. A process for producing an electrically conductive noblemetal thin film on a substrate in a reactor by atomic layer deposition,comprising: placing a substrate in a reaction chamber within thereactor; providing a vaporized noble metal precursor pulse into thereaction chamber to form no more than about a single molecular layer ofthe precursor on the substrate; removing excess vaporized noble metalprecursor from the reaction chamber; providing a second reactant gaspulse comprising oxygen to the reaction chamber such that the oxygenreacts with the precursor on the substrate; removing excess secondreactant gas and any reaction by-products from the reaction chamber; andrepeating until a thin film of a desired thickness is obtained.
 2. Theprocess of claim 1, wherein the second reactant gas comprises freeoxygen.
 3. The process of claim 2, wherein the free oxygen is molecularoxygen. 4 The process of claim 3, wherein the noble metal is selectedfrom the group consisting of ruthenium, rhodium, palladium, silver,rhenium, osmium, iridium, platinum and gold.
 5. The process of claim 3,wherein the noble metal precursor is selected from the group consistingof a metallocene compound and a beta-diketonate compound of the noblemetal.
 6. The process of claim 5, wherein the metallocene is selectedfrom the group consisting of bis(cyclopentadienyl)-ruthenium, aderivative of bis(cyclopentadienyl)-ruthenium,(trimethyl)methylcyclopentadienylplatinum and a derivative of(trimethyl)methylcyclopentadienylplatinum.
 7. The process of claim 5,wherein the beta-diketonate compound of the metal is selected from thegroup consisting oftris(2,2,6,6-tetramethyl-3,5-heptanedionato)ruthenium(III), a derivativeof tris(2,2,6,6-tetramethyl-3,5-heptanedionato)ruthenium(III),bis(2,2,6,6,-tetramethyl-3,5-heptanedionato)ruthenium(II) and aderivative of bis(2,2,6,6,-tetramethyl-3,5-heptanedionato)ruthenium(II).8. The process of claim 3, wherein the second reactant gas is providedby pulsing oxygen into the reaction chamber.
 9. The process of claim 3,wherein the second gas reactant is provided by pulsing a mixture ofoxygen and inert gas into the reaction chamber.
 10. The process of claim3, wherein the second reactant gas is provided by the catalyticdecomposition of an oxygen-containing chemical inside the reactor. 11.The process of claim 10, wherein the oxygen-containing chemical is H₂O₂or an organic peroxide.
 12. The process of claim 11, wherein thecatalytic decomposition is carried out using a catalyst selected fromthe group consisting of palladium and platinum.
 13. The process of claim3, wherein the second reactant gas is provided by forming oxygen insidethe reactor by decomposing N₂O.
 14. The process of claim 3, wherein agrowth initiating layer is provided on the substrate surface prior todepositing the noble metal thin film.
 15. The process of claim 14,wherein the growth initiating layer comprises hydroxyl groups.
 16. Theprocess of claim 15, wherein the growth initiating layer is an Al₂O₃thin film.
 17. The process of claim 15, wherein the growth initiatinglayer is a TiO₂ thin film.
 18. The process of claim 14, wherein thegrowth initiating layer has a thickness of between 10 Å and 20 Å. 19.The process of claim 14, wherein the growth initiating layer is producedby feeding H₂O₂ into the reaction chamber after placing the substrate inthe reaction chamber and prior to providing the vaporized noble metalprecursor pulse.
 20. The process of claim 3, wherein the noble metalthin film comprises a plurality of metals selected from the groupconsisting of ruthenium, rhodium, palladium, silver, rhenium, osmium,iridium, platinum and gold.
 21. The process of claim 20, wherein thenoble metal thin film comprises ruthenium and platinum.
 22. The processof claim 21, wherein the noble metal thin film comprises a firstportion, adjacent to the substrate, consisting essentially of ruthenium,and a second portion, over the first portion, the second portionconsisting essentially of platinum.
 23. A process for producing a noblemetal thin film on a substrate comprising: placing a substrate in areaction chamber; pulsing a vaporized noble metal precursor into thereaction chamber to form an adsorbed layer of the noble metal precursoron the substrate; removing excess vaporized noble metal precursor;converting the adsorbed noble metal precursor layer to a noble metallayer by contacting the substrate with a gas containing oxygen; removingexcess oxygen-containing gas and any reaction by-products; and repeatinguntil a thin film of the desired thickness is formed.
 24. The process ofclaim 23, wherein the oxygen is free oxygen.
 25. The process of claim24, wherein the oxygen is molecular oxygen.
 26. A process for producinga capacitor in an integrated circuit, comprising: depositing a firstinsulating layer on a silicon substrate having a doped region; forming aconductive material contacting the substrate through the insulatinglayer; depositing a barrier layer over an exposed surface of theconductive material; depositing a first electrode layer comprising anoble metal on the barrier layer by an atomic layer deposition process;depositing a second insulating layer on the first electrode layer; anddepositing a second electrode layer comprising a noble metal on thesecond insulator by an atomic layer deposition process.
 27. The processof claim 26, wherein the atomic layer deposition processes comprisealternately reacting the substrate surface with a vaporized noble metalprecursor and a gas comprising oxygen.
 28. The process of claim 27,wherein the oxygen is free oxygen.
 29. The process of claim 28, whereinthe oxygen is molecular oxygen.
 30. The process of claim 26, wherein thebarrier layer comprises a metal nitride layer deposited by atomic layerdeposition on the exposed surface of the conductive material.
 31. Theprocess of claim 30, wherein the barrier layer comprises tantalumsilicon nitride.
 32. The process of claim 26, wherein the secondinsulating layer comprises a layer having a high dielectric constantthat is deposited by atomic layer deposition.
 33. The process of claim32, wherein the second insulating layer comprises a layer selected fromthe group consisting of barium-strontium titanate and tantalum oxide.34. A method of producing an ultra-high density magnetic recordingdevice comprising: forming a first ferromagnetic recording layer on asubstrate; forming by an atomic layer deposition process a non-magneticlayer consisting essentially of a noble metal on the first ferromagneticrecording layer; and forming a second ferromagnetic recording layer onthe non-magnetic layer.
 35. The method of claim 34, wherein the atomiclayer deposition process comprises alternately reacting the substratesurface with a vaporized noble metal precursor and oxygen.
 36. Themethod of claim 35, wherein the thickness of the non-magnetic layer isbetween about 1 nm and 100 nm.